Fluorinated triazine monomers

Abstract

A compound of formula (I), wherein R1 and R2 are independently selected from saturated fluorocarbon substituted side chains, such as NR5(CH2)nCmF2m+1, O(CH2)nCmF2m+1, S(CH2)nCmF2m+1, NR5S(O)2(CH2)pCmF2m+1, or CR5[CO2(CH2)nCmF2m+1]2, where R5 is hydrogen or alkyl, n and m are independently an integer of 1-12, and p is 0 or an integer of 1-12, R3 is an unsaturate moiety which may be polymerised, and X is O, S or NR4 where R4 is hydrogen or alkyl, as well as methods for the preparation of these compounds. Compounds of formula (I) are useful monomers in the preparation of oil- and water-repellent polymers.

What is claimed is:  
     
       1. A compound of formula (I)                    
       wherein R 1  and R 2  are independently selected from NR 5 (CH 2 ) n C m F 2m+1 , O(CH 2 ) n C m F 2m+1 , S(CH 2 ) n C m F 2m+1 , NR 5 S(O) 2 (CH 2 ) p C m F 2m+1  or CR 5 [CO 2 (CH 2 ) n C m F 2m=1 ] 2 , where R 5  is hydrogen or C 1 -C 3  alkyl, n and m are independently an integer of 1-12, and p is 0 or an integer of from 1-12; R 3  is an unsaturated moiety which may be polymerized, and X is O, S or NR 4  where R 4  is hydrogen or C 1 -C 12  straight or branched chain alkyl or cycloalkyl. 
     
     
       2. A compound according to  claim 1  wherein R 1  and R 2  are the same. 
     
     
       3. A compound according to  claim 1  wherein R 1  and R 2  are selected from O(CH 2 ) n C m F 2m+1  or NR 5 S(O) 2 (CH 2 ) p C m F 2m+1 . 
     
     
       4. A compound according to  claim 1  wherein R 3  is a group of formula —(CH 2 ) q OC(O)CR 6 ═CR 7 R 8  where q is an integer of from 1 to 12, and R 6 , R 7  and R 8 are independently selected from hydrogen or a C 1-4  alkyl. 
     
     
       5. A compound according to  claim 4  where R 6 , R 7  and R 8  are all hydrogen. 
     
     
       6. A method of preparing a compound of formula (I) as defined in  claim 1 , which method comprises reacting a compound of formula (II)                    
       where R 1  and R 2  are as defined in  claim 1  and Y is a leaving group, with a group of formula (III)  
       
         
           R a —X—R 3′   (III)  
         
       
       where X is as defined in  claim 1  and R 3′  is a group R 3  as defined in relation to formula (I) or a precursor group which may be reacted to form a group R 3  and R a  is hydrogen or a C 1-3  alkyl group; and thereafter if necessary converting a group R 3′  to a group R 3 .  
     
     
       7. A method according to  claim 6  wherein R 3′  is a group of the formula (CH 2 ) q OH, and this is subsequently converted to R 3  by reaction with an acid halide of formula ZC(O)C(R 6 )═CR 7 R 8  where Z is a halogen and R 6 , R 7  and R 8  are as defined in  claim 5 , in the presence of a base. 
     
     
       8. A method according to  claim 6  wherein the compound of formula (II) is prepared by reacting a compound of formula (IV)                    
       where R 1  is as defined in relation to formula (I), Y is as defined in relation to formula (II) and Y′ is a leaving group, with a compound of formula (V)  
       
         
           R 2 H  (V)  
         
       
       where R 2  is as defined in relation to formula (I), in the presence of a base.  
     
     
       9. A method according to  claim 8  wherein the compound of formula (IV) is prepared by reacting a compound of formula (VI)                    
       wherein Y, Y′ and Y″ are the same or different leaving groups, with a compound of formula (VII)  
        R 1 H  (VII) 
       where R 1  is as defined in  claim 1 , in the presence of a base.  
     
     
       10. A method according to  claim 9  wherein the compound of formula (IV) is converted to a compound of formula (II) in situ. 
     
     
       11. A polymeric compound which has been derived from a compound of formula (I) of  claim 1 . 
     
     
       12. A polymeric compound according to  claim 11  which comprises a polymer or copolymer including repeating units of formula (VIII)                    
       where R 1 , R 2  and X are define in relation to formula (I), t is an integer in excess of 5, and R 9  is a saturated derivative of R 3  as defined in relation to formula (I).  
     
     
       13. A polymeric compound according to  claim 12  wherein XR N  is a moiety of formula (IX)                    
       where q, R 6 , R 7  and R 8  are as defined in  claim 4 .  
     
     
       14. A substrate which is coated with a polymeric compound according to  claim 11 . 
     
     
       15. A substrate according to  claim 14  which is a fabric.